Sulphonated fatty oils and method of making same



Patented Jan. 9, I

The present invention relates to the process or.

preparing,esulphonamd o-ils andl-it particularly relates tojimproved sulphonated fatty. oils which f n k are produced thereby.

" The commercial sulphonated oils are ordinarilyproduced by reaction between sulphuric acid ,or

a similar sulphonating agent and a saponifiable oil or fat, or their fatty acids, ormiXtures-there of. These'sulphonated oils'usually containfa' substantial amount or undesirable impurities which apparently are produced in the course of the sulphon'ation reaction. p

These ir'npurities cause gradually forming sludges or-precipitates which may in part settle out after standing fir storage or remain suspended'for' long periods of time as a cloud or haze.

Itis famong theobje'cts of the 'aresentinvention togprovide a process of producing" improved sulphonate'd compounds of the ,"character dej gradually s assumes adefiniteemulsion, the addiscribed in which the final product willbe a clear bright liquid, substantially-devoid of precipitate or sludge: forming constituents and which will have ahigh SO: content, --.allwithout the need of carrying "special sulphonation"processesloremploying special catalysts-or special reagents Other-objects will be obvious or will appear during the' 'c'ourse of the following specification.

Thesev sludge or precipitate formingcompounds appear to be generally unsulpho-nated oily, fatty or lfatty'acid materialsiwhich have notlent-er'ed into or'do not readily enter into -the;'sulphona- ,tion'reactionand which not only render result:

.ing sulphona-ted oil hazy-and cloudyand of low" quality, but 'in additionf result in a decreased S03 content, l

It has been found that these unsulphonated' fatty or oily materials generally consist of the saturated 7 ,fatty acidsv or glycerides, such as p'almitin, stearin, or laurin, or i the corresponding '5 fatty acids, palmitic, steari'c and'lauric, which are not readily sulphonated and also include some of unsaturated acids or g1ycerides,fsuch as olein, oleic acid, and so forth,.then'iajor portion.

from the sulp-honated product-to produce a fink ished'oil havingapermanently clear and pleas' ing appearance and of high quality;

v Thislpu rification may be most readilylaccoin plished bythe adclitioncf an alkaline agent and preferablyuaistrong alkalhsuCh as sodium hy droxida toe the sulphonated oil irnmediatelyaiter sumea clearappearance'.

Application February25,@1936; 1 ;SerialN0. 65',643 '2; ,14 mai (01. 2 0.400)

' sulphonatingi so' that the oil wi11 'hayefiaof 10 to 12 0i higher. j

Thesodium'hydroxide'or other alkali so added I i should be used; in quantity over and, above that normallyutilized in" finishing the sulphonated oils. This over; alkalization'will result -i n-"a" precipitation 'andfithrowinyout of the objectionable un-" Sal-paneledmemes including u ch a i sulph'onated saturated r'c ompo und's. Apparently the equilibrium of up by=-the1excessfqiiantity of alkali'with resultant pr'ecipitation;- Y L l;

The -.alkali should be added gradually to the sulphonated eii m secure the precipitation and removal of these und'esirable constituents" followed; by vigorous agitation after each addition;

;Whe' n tion and agitation Zniay be discoiitinuedfi' a sludge like mass often containing an oily 's'uroil) : jter thisi oilylsludge has f'o-rmed n v hlst rfaee' fthe-mai-n"body of oil thereunder will' as- 'Ih eY-upper'slfdg e layer u eliminating, the undesirable g-unsulrihonated im-' may then be r-ei'noved af'elouding,- eifect is ob'servedfl-which throughla settling; or ageing period, atgynor nal ofse'levat'ed ternperaturesgduring wh ch period 25 1 face layer will gradually rise to the top of the I purities and thelowerlayer of. clear oilinayvthen I .be treated to reduce :its' alkali clontent which is sdr'newhatiri excess of that suitable: for 'ordinary usage. 7 a e "To r'educe thegamount of alkali," the lower layer may beneutrali'zed with a-mineralgor organic jnite alkalinity fw'illuresult dependent upon" purposes for which the oil is to be utilized.v 1

Forv ,textile -finishing, for exainp1e,;'the sulphonatedfinishedjand purified oil should' have'i Of which unsaturated compounds has b en sul-f a about degumml'ng a pH about phonated- H 4 It has .nOW b'een discovered that these unsul':

phonate'ddcomponents may lie-readily removed r 10; or for'usefincosnf etics a pH ofabout"'7.

' ,fIhe ,cil mayalso e slightly acidified with ,a mineral f or organic acid followed by "treatment and agitation with an aqueous 's alt solution; such asa'solution of sodiumchloride-or sodium s u1 phate. "After thepm'asb has separated, the aqueous solution is drawn ofi'and theexcesslacid remain,-

ing in the oil is neutralizedwith"alkali. addition of alkali'c'ontinued untilgthe 'desired combined alkali content isobt'ained.

Example A sulphonated olive oil is prepared by adding 1600 parts of strongsulphuric acid (say 66 B. or 98%) slowly to 4000 parts of olive oil. 7 Other sulphonating agents such as chlorsulphonic acid or fuming sulphonic acid may also be employed.

The mixture during the addition is well stirred i and the temperature is controlled either by the rate of addition of the acid or by artificial refrigeration or by both so that the temperature.

does not exceed 35 C. at any time. The mixture is agitated for 8 to 12 hours after the addition. Then the mixture is treated with an aqueous salt solution fort example containing sodium chloride or sodium sulphate. p

The oil is then allowed to settle, the aqueous acid-salt layer is removed and the residual acid in the oil is then neutralized with alkali.

This neutralization process is-continued beyond the-point at which the mixture begins to cloud or to show free alkali, as indicated by reddening upon addition to an alcoholic solution of phenol phthalein. i At this point, the oil being treated assumes an emulsion like appearance, which may be enhanced \by the addition of a small quantity of water if the oil is too concentrated. The ad.-

vdition of alkali should always be continued until ageing period;

The lower portionof the aged mixture containing the. refined and purified sulphonated oilmaybe treated with a mineral or organic acid to. reduce the alkali content to neutrality or. to. acidity. Acidification should be followed bywashing with a salt solution and then neutralization with alkali to the proper'alkali content.

Instead of the proportions above, 'it is also possible toadd 1500 parts of the 60 B. sulphuric acid to 4000 parts of olive oil. I

Withcastor oil, from 1200 to.1300 parts of 66 B. sulphuric acid may be employed for every 4000 parts ofcastor oil. 1 v With corn oil, from 1500 to 1600 parts-of 66. B. sulphuric acid may be used for each 4000 parts of corn oil.

Amongthe other-oils which may be utilized are menhaden oil, palm oil, mustard seed oil, pea seed oil, linseed oil, cottonseed oil, rape seed oil, castor oil, Neats foot oil, peanut oil, lard oil, tallow oil,

elaine oil, corn oil, sperm oil, and/or fish oil or,

their fatty acids or mixtures thereof.

The oils should contain substantial or large quantities of unsaturated aliphatic acids, and particularly olei'c'a'cid or its glyceride, olein, but linseed oil or other. oils containing glycerides of linoleic acid,.linolenic acid, ricinoleic acid, and eleostearic' acid may also be used. Preferably the saturated gl cerides, such a stearin, palmitin, laurin and so forth or their fatty acids should be sludge as .an upper layer. i 1

present in only, minor quantities, since they cannot be sulphonated by the above procedures, but only by turning sulphuric acid at elevated temperatures and pressures.

The proportionsgiven above may be considerably varied but generally about 20 to 50 lbs. of 66 B. H2804 should be used for every 100 lbs. of the oil, with an optimum of about 30 lbs.

In the alkalized oil there should be quantities of free alkali-present, but in the finished oil the alkali present, should. onlyv be sufficient to neutralize substantially all of the sulphonic. acid groups. p H

l-lowever, there' should be insufficient alkali present in the alkalized oil to saponify the unsulphonated oiland fatty materials which are tion or proportions, or to any particular applica- .tion, or to anyspecific manner of. use, or to any of various details thereof, herein described; as

the same may be modified in various particulars.

or be applied in many varied relations without departing from the spirit and scope of the claimed invention, the practical embodiments herein decomprises reactinga fatty. oil with'sulphuric acid to produce the sulphonated oil, treating the reaction mixture with an aqueous salt solution, settling to permit formation of an aqueous layer, separating the aqueous layer from the sulphonate ed product, alkalizing the sulphonated product,

said alkalizing being accomplished by thegradual addition of an alkali with agitation untilan actual definite clouding is accomplished, the ad-- dition' of alkali being stopped substantially bejusting the alkalinity of the refined oil, said mix ture being permitted .to stand at a temperature not exceeding- C. during the separation of the 2. A process of making a sulphonated oil which comprises reacting a fatty oil with sulphuric acid to, produce the sulphonated oil, treating the reaction mixture with an aqueous salt; solution, settling to permit formation of an aqueouslayer, separating the aqueous layer from the sulphonated product, alkalizing the sulphonated product only until the sulphonated product becomes cloudy,- f said alkalizing being accomplished by gradually adding caustic soda with agitation followed'by standing of the material until the sludge containing unsulphonated oils and fatty acids I separates an upper layer separating the sludge of the refined and then adjusting the alkalinity oil. r

-3. A process of making a sulphonated oil which comprises reacting a fatty oil 5 with sulphuric acid to produce the sulphonated oil, treating the reaction mixture with an aqueous salt solution, settling to permitformation of an'aqueous layer,

separating the aqueous layer from the sulphonat' ed product, alkalizing the sulphonated product tion and then permitting 1 the mass to settle or age until an upper layer of sludge containing the unslilphonated oils'and fatty acids forms, sepa-. rating the sludge and then adjusting the alkalinity of the refinedoil. -4 A process of making a sulphonated oil which comprises reacting oliveoil withsulphuric acid to produce the sulphonated oil, treating the re- 1 actionf mixture with" an aqueous salt solution, settling to permit formation of an aqueousl'ayer, separating the aqueouslayer from thesulphonat- 1 ed product, alkalizing the sulphonated' product,

' said alkalizing being accomplished by the gradual until the sludge containing the unsulphonated.

oils and fatty acids separates as'an upper layer, separating the upper sludge layer and then adjusting the alkalinity of the refined oil, said vmixture being permitted to stand at a temperature not exceeding 75 C. during the separation.

of the sludge as an upper layer.

5. A process of making a sulphonated oil which comprises reacting castor oilwith sulphuric acid to produce the sulphonated oil, treating the reaction mixture with an aqueous salt solution, settling to permit formation of an aqueous layer, separating the aqueous layer from the sulphonated product, alkalizing the sulphonated product, said alkalizing being accomplished by the gradual addition of an alkali with agitation until an actual-definite clouding is accomplished, the addition of alkali being stopped substantially before sufficient alkali is added to saponify the unsulphonated oils, permittingthemixture to stand until the sludge containing the unsulphonated oils and fatty acids separatesas an upper layer, separating the. upper sludge layer and then adjusting the alkalinity of the refined oil, said mixture being permitted to stand at a temperature not exceeding 75 CQ duringjtheseparation, of

the sludge as anupper layer.

.6. A process of making a sulphonated oil which comprises reacting a corn oil with sulphuric acid to produce the sulphonated oil, treating the reactionmixture with an aqueous salt solution, settling to permit formation-of an aqueous layer, separating the aqueous layer from the sulphonat- 'ed product, alkalizingthe sulphonated product,

saidalkalizing being accomplished by the gradual addition ofan alkali with agitation until an actual definite clouding is accomplished, the addition of alkali being stopped substantially before sufficient alkali is added to saponify the unsulphonated oils, permitting the mixtureto stand until the sludge containing the unsulphonated oils and fatty acids separates .as an upper layer, separating the upper sludge layer which forms and then adjusting the alkalinity of the refined. oil,

saidmixture being permitted to stand at a temperature not exceeding 75 C. during the separation of the sludge as an upper layer.

'7. A process ofpurifying a sulphonated fatty oil and thereby removing unsulphonated oily, fatty or fatty acid materials, which comprises adding an alkali thereto until the mixture is definitely alkaline and becomes cloudy, agitating the alkalized mixtureafter each addition of alkali, permitting it to stand for several days and then removing the layer of sludge containing the unsulphonated oil, fatty or fatty acid materials which forms at the top.

alkali.

andther eby removing unsulphonatecl-oily, fatty.

or fatty acid materials,;whichcomprises adding caustic soda thereto until. the r'nixture becomes "cloudy'but stopping the addition before there is sufficient caustic'soda added to'saponify the un stand at a temperature between 35"" to C. for between 12 to 96 hours andthen separating the vsulphonated oil, the mixture being vigorously agitated after each addition, permitting it to layer-of sludge containng fth'e 'un'sulphonated oil, 7

fatty or "fatty acid materials which for'ms at the top of thesulphonated mass. 9. A process of purifyingasulphonated 'oil and thereby removing unsulphonated oily, -fatty 'orfatty acid materials, which comprisesalkalyizj ing the sulphonated oil with caustic soda, said caustic soda being added gradually until an actual definite clouding is accomplished,but the addition being stopped before there is sufficient alkali to saponify the unsulphonated oil and, fatty materials, agitating the. mixture, permitting it to stand, removing the layer of sludge containing the unsulphonated oil, fatty-or; fatty acid ma- 3138113118 whichforms at the top thereof andthen adjusting the alkalinity of "the product.

10. A process of purifying a sulphonate d oil andthereby removing unsulphonated oily, fatty.

or fatty acid materialauWhich comprises alkalizing thesulphonated oil with caustic soda,

said caustic soda being added gradually until an actual definite clouding is accomplished, but the addition being stopped before there is sufficient alkali to saponify the unsulphonated' oil and fatty materials, agitating the mixture, per- Initting it to stand-removing the layer of sludge containing the'unsulphonated oil, fatty or fatty acid ,materials which forms at the top thereof and then adding an acid to reducethe alkali content. I P f 11.,A process of purifying a sulphonatedoil and thereby removing unsulphonatedv oily, fatty or. fatty acid materials which comprises alkalizing the sulphonatedbil with caustic soda,said caustic soda being added gradually until an actual definite clouding is accomplished, but the addition being stopped before there is sufficient alkali to saponify the unsulphonated oil and 7 fatty materials, agitating the mixture, permitting it to stand, removing the layer of sludge containing the unsulphonated oil, fatty or fatty acid materials which forms at the top. thereof and then acidifying and washing with an aqueous .salt solutionand finally neutralizing with an alkali. 4 v

12. A process'of purifyinga sulphonated oil and thereby removing .unsulphonated oily, fatty or fatty acid materials, whichfcomprises alkalizing the sulphonated oil with caustic soda,*'said caustic soda being added gradually until an actual definite clouding-is accomplished, but the addition being stopped before there is sufiicient alkali to saponify the unsulphonated oil and fatty materials, agitating the mixture, permitting it to stand, removing the layer of sludge containing the unsulphonatedofl; fatty or fatty acid materials which forms at the topthereof, then acidifying the oil, treating the oilwith a sodium salt solutionyremoving the solution after sepa-' ration and then neutralizing the excess acid with 13. The process of preparing a sulphonated olive oil which comprises adding 1600 parts of strong sulphuricacid slowly to 4000 parts of olive oil with stirring, controlling the temperature so that itdoes not exceed 35 C., agitatingthe mass from 8 to 12 hours, mixing with an aqueous salt solution, settling and then drawing ofi the aqueous acidic salt layer, neutralizing the residual acid in the oil with an alkali, continuing the addition of the'alkali until the mixture begins to cloud, and then stopping the addition of the alkali so that there will be insufficient alkali present to saponify the unsaturated oil and fatty materials, again agitating, permitting the mixture to standfor two or three days, removing the layer of sludge containing the unsulphonated oil, fatty or fatty'acid materials which forms at the top of the mass and then adding an acid to reduce the alkalinity of the resultant oil.

14. The process of preparing a sulphonated olive-oilwhich comprises adding strong sulphuric acid slowly to olive oil with stirring, agitating the mass, mixingwith-an aqueous salt solution, 

